JPH04258615A - Composition containing emulsified copolymer comprising alkylacrylamide, glycolate alkyl ether and monomer containing vinyl acetate and hydroxy functional group - Google Patents

Abstract

PURPOSE: To provide a one-pack type polymer emulsion which is suitable for use as adhesive and binder and does not generate formaldehyde during curing.

CONSTITUTION: This emulsion is obtd. by emulsion copolymn. of an alkylacrylamide glycolate alkyl ether (MAGMA), vinyl acetate and a functional hydroxide-contg. monomer under a condition where homopolymn. of MAGME is avoided.

COPYRIGHT: (C)1992,JPO

Description

[Detailed description of the invention]

The present invention relates to compositions of emulsion copolymers comprising at least one alkylacrylamide glycolate alkyl ether, vinyl acetate, and hydroxy-functionalized monomers.

In particular, the present invention provides the formula

0003

[Case 2]

##STR1## where R1 is hydrogen or methyl, preferably hydrogen, and R2 and R3 are independently C1-C6 alkyl and C5-C6 cycloalkyl, preferably C1
Concerning special uses of alkylacrylamide glycolate alkyl ethers, which are selected from -C4 alkyls.

The use of such glycolate ethers of formula (I) in the polymer field is generally known and is described, for example, in US Pat. No. 4,522,973. The US patent relates to a low temperature crosslinkable emulsion consisting of a polymer containing repeating units derived from monomers having formula (I) and a crosslinking agent having a large number of primary amine groups. Unsaturated copolymerizable repeating units, such as alkyl esters of acrylic and methacrylic acid, styrene,
Repeat units of vinyl acetate, butadiene, ethylene, cyclopentadiene, acrylonitrile and vinyl chloride may also be present. A preferred compound of formula (I) is methylacrylamide from American Cyanamid.
Glycolate methyl ether (MAGME). A significant drawback of the emulsion polymers described in that US patent is the use of a two-part system. Furthermore, it is necessary to cure with amine. This is because sufficient self-crosslinking does not occur simply by heating. According to the example, MA
GME requires relatively high concentrations. Also, the patent does not mention the use of hydroxyl functional groups.

European Patent A-0 302 58
No. 8 includes formaldehyde prepared by polymerizing the compound of formula (I) with a copolymerizable monomer, such as acrylic acid and methacrylic acid (or their esters), styrene, and vinyl esters such as vinyl acetate. Binder compositions are described that do not contain. The composition may also contain reactive functional groups such as hydroxy, carboxy and amino groups. MAGME is used in the examples, but not in combination with vinyl acetate.

European Patent A-0 218 82
No. 7 describes formaldehyde-free polymers in which compounds of formula (I) can be used. The patent states that "acrylamide/glyoxylic acid condensates and their ethers and esters were used. These materials do not perform well in applications with vinyl acetate/ethylene emulsions...".

The use of compounds of formula (I) is further described in US Pat. No. 4,743,498 [Kedrowski
Kedrowski)], No. 4 454 301
No. [Caddy], No. 4 778 8
No. 69 [Schirmann], No. 4
656 No. 308 (Sherman), No. 4 4
No. 89264 [Fink].

The properties and uses of MAGME are summarized in a leaflet entitled ``MAGME*100, Multifunctional Acrylic Monomer'' published by the Polymer Production Division of American Cyanamid Company. The following table is included on page 5 of this leaflet.

0010

[Table 1] Copolymerization parameters of MAGME and various vinyl monomers Monomer I Monomer II r1
r2MAGME styrene
0.21±. 3 0.
36±. 4 Acrylonitrile 0.66±. 32 0.67±
．． 24 Methyl methacrylate 1.27±. 32 0.95±. 20
butyl acrylate
3.10±. 19 1.03±. 04
Ethyl acrylate 3.
26±. 25 0.78±. 04
Vinyl acetate 38.2
±3.2 0.10± . 03 Based on the above copolymerization parameters, experts in the field of emulsion polymerization would generally give up on combining MAGME with vinyl acetate.

According to the invention there is provided a composition with surprising properties comprising a copolymer of a compound of formula (I), vinyl acetate and a monomer containing at least one hydroxy functional group. According to the present invention, various drawbacks of conventional methods are overcome.

The present invention relates to the total weight of the composition: (a)
formula

[0013]

[Chemical formula 3]

An alkylacrylamide glycolate of the formula wherein R1 is hydrogen or methyl, preferably hydrogen, and R2 and R3 are independently selected from C1-C6 alkyl and C5-C6 cycloalkyl.
0.1-25% by weight of alkyl ethers, (b) 50-95% by weight of vinyl acetate, (c) 0.1-25% by weight of monomers with one or more hydroxy functional groups, (d) The present invention relates to a composition characterized in that it contains 0 to 50% by weight of other vinyl monomers.

Preferably, the composition of the invention contains 0.5 to 10% by weight of component (a) and 0.5 to 10% by weight of component (a), relative to the weight of the total composition.
It contains 80 to 90% by weight of b), 0.5 to 10% by weight of component (c), and 5 to 20% by weight of component (d).

In particular, in the composition of the present invention, component (a
) is methyl acrylamide glycolate methyl ether (MAGME), component (c) is selected from the group consisting of 2-hydroxyethyl acrylate (2EHA) and/or hydroxyethyl methacrylate (HEMA), or polyols, polyvinyl alcohol and cellulose compounds. and component (d) is an alkyl ester of acrylic acid, methacrylic acid or maleic acid, such as butyl acrylate (B
A), methyl methacrylate (MMA), dibutyl maleate (DBM), vinyl chloride, vinylidene chloride, butadiene, ethylene and/or propylene.

Surprising and important properties of the compositions of the invention are: - formaldehyde-free system;
- the cured product has a high degree of solvent and water resistance; - good adhesion to substrates such as polyester; - excellent gloss.

Since component (a) (eg MAGME) is not made from compounds derived from formaldehyde, there is no possibility of formaldehyde being released from the crosslinked film under acidic and curing conditions.

It is known in the art that vinyl acetate (component b) is hydrophilic and copolymers of vinyl acetate have poor water and solvent resistance. It is therefore surprising that the compositions of the present invention, which are predominantly composed of vinyl acetate units, have solvent resistance. The curing time of the film of the composition of the present invention is very short, for example at pH 1.
5 to 3 for 5 minutes/130°C.

In the step of copolymerizing the monomers to obtain the composition of the present invention, component (a) is gradually added in such a way as to avoid homopolymerization of MAGME (power supply addition method). The rate of addition is calculated and determined using reactivity parameters. When MAGME is used as component (a), the MAGME addition rate is determined by the reactivity ratio r1 and r
2, and its concentration in the monomer mixture. The dosing system corresponds to the power delivery dosing calculations below and Tables A, B and C below are based thereon.

[0021]

[Math 1]

[0022]

[Math 2]

[0023]

[Math 3]

where: M1 = amount of MAGME in feed A (g or moles) M1b = amount of MAGME in feed B (g or moles) M2 = amount of VA in feed A (g or moles) M2b = Amount of VA in feed B (g or moles) A = Content of feed A (g) BO = Initial content of feed B (g) Va =
Addition rate of Feed A (g/min) Vb = Addition rate of Feed B (g/min) δt = Time interval used for calculation (min) The "MAGME" column shows the MAG added to the reactor.
The total amount of ME is listed.

r1 and r2 are copolymerization parameters of the MAGME/VA system.

[0026]

[Table 2]

[0027]

[Table 3]

[0028]

[Table 4]

As is clear from the above description, in order to obtain a composition with good properties in the present invention, various polymerization reactivities of various monomers must be taken into account. However, the above calculations allow the metering system to be easily adjusted.

Polymerization methods are well known in the art. Preference is given to using emulsion polymerization methods in aqueous media. The present invention also provides
The present invention relates to a process for the preparation of novel polymer compositions, characterized in that component (a) is added to the polymerization medium in such a way that it is uniformly distributed over the backbone of the polymer. As is clear from the above description, a power supply system is preferred.

A variety of free radical generating initiators can be used in catalytically effective amounts. Generally, these initiators are not critical to the polymerization or performance characteristics of the compositions of this invention. Examples of reaction initiators are organic or inorganic peroxides or azo compounds. It is also possible to use combinations of reducing and oxidizing agents, for example t-butyl hydroperoxide/sodium metabisulfite.

Particular preference is given to using inorganic redox systems such as ammonium, sodium or potassium persulfate in combination with sodium metabisulfite at polymerization temperatures of 50 to 65°C. It is also possible to use persulfates alone at reaction temperatures of 65-80°C. Obviously, it is undesirable to use sodium or zinc formaldehyde sulfoxylates, which cause formaldehyde release, or azo-based reaction initiators, which have poor crosslinking performance. The amount of peroxide used in the system of the invention is well known to emulsion polymerization experts and is generally 0.01 of the amount of monomer used.
-1% by weight, preferably 0.05-0.5% by weight.

Various emulsifiers can be used in the polymerization system. For example, it is possible to use ionic and/or nonionic surfactants such as sodium lauryl sulfate, sulfonated alkylbenzenes, phosphoric esters and alkylphenoxypolyethoxyethanols or polyoxyethylene condensation products. Typical emulsifiers that are very suitable for the polymerization systems of the present invention include Aerosol® A-102 (American Cyanamid, disodium ethoxylated alcohol half ester of sulfosuccinic acid), Aerosol® A
103 (manufactured by American Cyanamid, disodium alkylaryl ethoxylated alcohol half ester of sulfosuccinic acid) and ethoxylated nonylphenol (2
(0 to 40 moles of ethylene oxide) or an Aerosol(R)-102/MA80 mixture.

In addition to or instead of emulsifiers, protective colloids such as polyvinyl alcohol, hydroxyethyl cellulose can be used. Typical buffer systems include sodium bicarbonate or diammonium hydrogen phosphate;
Alternatively, other synthetic colloids may be included.

The amount of surfactant is usually from 0.5 to 5% with respect to the weight of monomer.

Buffer systems can be used to maintain the pH of the reaction medium at the desired value.

The invention also relates to the use of the novel compositions of the invention as binders, coatings or adhesives. Such binders are suitable for use as formaldehyde-free crosslinking agents in woven and nonwoven fabrics, paper coatings, diaper raw materials, hand towels, towels and rug materials. In a preferred embodiment, the present invention provides that the copolymer (
a) 0.5-10% by weight MAGME and (b) 50
A self-crosslinking binder as defined above containing ~95% by weight vinyl acetate.

The invention is illustrated by the following Examples 1-18. Examples 1-8 illustrate a conventional emulsion polymerization process, and Examples 9-18 illustrate the homopolymerization of MAGME in the aqueous phase, so that polymerization with itself on the growing copolymer chain is avoided. An example (power supply system) in which MAGME(R) is gradually added and used is illustrated.

The following latex was prepared using a conventional semi-batch emulsion polymerization method.

VA/BA/NMA 86/12/2 weight ratio


Weight (g) A. Charge material to reactor Deionized water

110.0 Aerosol(R)A-
102 (31%)
6.7 NaHCO3 (sodium bicarbonate)
1.0 methanol

5.0 Ammonium persulfate
2.0B.
Monomer preemulsion vinyl acetate (VA)
1
72.0 Butyl acrylate (BA)

24.0 Aerosol (R) A-10
2 (31%)
6.7 Sodium metabisulfite

0.4 methanol

5.0
deionized water
6
5.0C. Retardation part N-methylol acrylamide (NMA)
, 48% 8.4 Deionized water
10.
0 initial charge to the reactor and sparge with N2 for 15 minutes while warming to 65°C. Add 15% of the monomer preemulsion to the reactor at 65°C. After the reaction has started (blueish in color), the NMA solution is added to the pre-emulsion mixture. The remaining monomer preemulsion is gradually added to the reactor over a period of 3 hours. The mixture is kept at 65° C. for an additional hour after the addition is complete. The resulting latex is cooled to room temperature, filtered and placed in a suitable container.

[0041]

Examples Examples 2, 3, 4 Example 1 was repeated except that the following mixture was used as the monomer mixture.

[0042]

[Table 5]
1 2
3 4 VA
172 172
172 172 BA
24
24 24 24
NMA (48%) 8.4
-- 8.4 --
― MAGME (R) ―
6.45 --
6.45 HEMA
―― ――
4.6 4.6 Examples 5, 6,
7,8 Example 1 was repeated except that the following mixture was used as the monomer mixture.

[0043]

[Table 6]
5 6
7 8 VA
172 172
172 172 BA
24
24 24 24
NMA (48%) 16.8
-- 16.8 --
MAGME(R) --
12.9 ---
12.9 HEMA -
― ― 9.
2 9.2 Example 9 In this example, MAGME(R) was gradually added (power (supply) was used.

Power supply VA/BA/MAGME/HE
MA Emulsified Latex The monomer mixture of Example 8 was repeated except that the method described below was used.

[0045]

Weight (g) A. Charge material to reactor Deionized water

110.0 Aerosol (R) A-10
2 (31%)
6.7 NaHCO3 (sodium bicarbonate)
1.
0 methanol

5.0 Ammonium persulfate

2.0B. Monomeric power supply additive (1) VA

86 BA

12 HE
M.A.
1
MAGME(R)

2 (2) VA

86 BA

12H
EMA
8.2
MAGME(R)

10.9 Methanol

5.0C. Catalyst added Deionized water

75 Sodium metabis sulfite

0.4 Aerosol (R) A-10
2 (31%)
6.7 Charge the initial charge to the reactor and sparge with N2 for 15 minutes while warming to 65°C. At 65°C 15% of monomer charge B(1) is added to the reactor. After the reaction has started (bluish in color), the remaining monomer B(1) is gradually added to the reactor over a period of 3 hours, during which time B(2) is continuously added to the monomer mixture B(1). ). At the same time, the catalyst solution is added over a period of 3 hours. After the addition is complete, stir the mixture for an additional hour at 65°C.
The latex is then cooled to room temperature and filtered into a suitable container.

Examples 10, 11, 12 Time V for monomer mixtures B(1) and B(2)
Example 9 was repeated except that calculations were made from the A/MAGME reactivity ratio.

[0047]

[Math 4]

[0048]

[Table 7] B(1)
10 11
12 VA
43 43
43 BA
6
6 6 MAGME
(R) 4
2.6 1.3 H
EMA 2.5
1.6 0.8B
(2) VA 12
9 129 129
BA 1
8 18 1
8 MAGME(R)
8.9 6.0
3.0 HEMA
5.7 4.6
2.3 Example 13 A latex having the following composition was prepared.

[0049]

[Table 8]
Example 13 Example 14 Example 15 A. Reactor charge Deionized water 111.0
111.0 111.0
FeCl3 1% 0.85
0.85 0.
85 Formic acid
0.055 0.055
0.055 Aerosol (R) A-102, 31% 9.7
9.7 9.
7 Methanol 5
．． 0 5.0
5.0 Potassium persulfate
1.0 1.0
1.0 Initial monomer VA 1
6.0 16.0
16.0 BA
2.0 2.0
2.0 MAGME(R)
0.3
0.3 0.3 Sodium metabisulfite 0.1
0.1 0.1 Deionized water
10
10 10 Power supply-monomer addition B(1)
13 14
15 VA
50 50
50 BA
8
8 8 M
AA 0.6
0.6
0.6 MAGME(R)
2.0 2.6
2.0B (2) VA 100
100 1
00 BA
16 16
16 MAA
1.4 1.4
1.4 MAGME(R)
5.5
5.5 5.5 Methanol 5.0
5.0 5.0C
) Catalyst addition Deionized water 65
65
65 SMBS
0.5 0.5
0.5 Sodium bicarbonate
0.9 0.9
0.9 Diammonium hydrogen phosphate 0.3
0.6
1.0 Aerosol(R) MA-80 (80%) 2.
5 2.5
2.5 Charge the initial charge to the reactor and sparge with N2 for 15 minutes while warming to 65°C. The contents of the polymerization tank are 60
Once the temperature is reached, the nitrogen flow is reduced to a minimum and the initial monomer mixture and starting catalyst are added to the reactor. After the reaction has started (bluish in color) and maximum exotherm has occurred, monomer and catalyst additions are started at a rate of 1.5 and 0.4 parts per minute, respectively. After the monomer and catalyst additions are complete, the latex is held at 60° C. for an additional hour, then cooled to room temperature, filtered and placed in a suitable container.

Examples 16, 17, 18 Example 13 except that hydroxyethyl methacrylate (HEMA) monomer was included and the following monomer mixture was used in the addition of B(1) and B(2). repeated.

[0051]

[Table 9] B(1) Example 16 Example 17 Example 18
V.A.
50 50
50 BA
8
8 8 MAA
0.6
0.6 0.6
MAGME(R) 2
．． 0 2.0
2.0 HEMA
1.4 1.4
1.4B(2) VA 1
00 100 10
0 BA
16 16
16 MAA
5.5 5.5
5.5 HEMA
4.0
4.0 4.0 Methanol 5.0
5.0 5.0 Example 19 The emulsions obtained in Examples 1 to 18 had the following physical properties (Tables 1 and 2). This is equivalent to the conventional latex used industrially.

Example 20 The emulsions of Examples 1 to 18, with or without various subsequently added catalysts, are filmed on Melinex polyester film (100 mμ) using a 100 mμ coater. The film is air dried (ie, 18-24 hours at room temperature) and then cured in an air reflux oven at 130°C for 3 and 5 minutes.

The cured and uncured films were treated with acetone insolubles and solubles (ie, indicators of solvent and cleaning resistance) and methyl ethyl ketone (M
EK) The swelling coefficient was tested by the following method.

Method for measuring the acetone-insoluble content of films Films with and without catalysts each having a thickness of about 100 mμ are placed on a glass plate and dried at 25° C. for 24 hours.

Divide the film into three samples of about 1 g,
Cure at 130° C. for 0, 3 and 5 minutes, respectively. The sample was then accurately weighed, cut into small pieces, and 1
Reflux in 00.0 ml of acetone for 2 hours.

After cooling the acetone, fold Whatman filter paper No. 1 into a (closed) bottle. 540 and filter the liquid.

A 10 ml sample is taken from the filtrate and weighed accurately, after which the insoluble content can be calculated from the following formula.

[0058]

[Math 5]

However, I = Insoluble content of the film (%) F = Weight of the film (g) S = Weight of the soluble content (g) Swelling ratio and MEK insoluble content measurement method Dry a film of approximately 100 mμ for 24 to 28 hours. let 2.0 x 2.0 cm (70 to 200 m) from this film.
Cut out the sample g), weigh it accurately (W1), and weigh it at 130
Cure for 0 and 5 minutes. 6 in MEK
After soaking for 0 minutes, the sample was dried by sandwiching it between tissue paper, placed in an aluminum dish, and weighed again (W2).
Dry at 130°C for 30 minutes and finally weigh again (W3
).

[0060] Swelling ratio = W2/W1 insoluble content (%)
= W3/W1 × 100% Tables 3, 4, 5
Acetone-insoluble content for the films of Examples 1 to 18,
and MEK swelling index and MEK insoluble content data. These results show that the copolymer of vinyl acetate and MAGME produced by the present invention undergoes self-crosslinking and gives results comparable to conventional products, but contains no or a very small amount of formaldehyde (i.e., 1 ~10 ppm).

[0061]

[Table 10]

a: #100-135: 2 phm Aerosol A102
1.5phm AP
0.2 phm Aerosol MA80 #146-159:
1.5 phm Aerosol A102
0.5 phm aerosol MA80
KP of 0.5 phm
0.3p
hm SMBS, FeCl3/Formic Acid All batches contain 51% solids.

b: molar ratio of monomers c: molar concentration (%) of added MAGME and HEMA d: E = added preemulsion type P = added power delivery solution type e: N = sodium bicarbonate P = diammonium hydrogen phosphate 2P = diammonium hydrogen phosphate, 2 times the amount 3P = diammonium hydrogen phosphate, 3 times the amount f: Use NMA instead of MAGME

[0064]

[Table 11]

[0065]

[Table 12]

1: Adjust pH to 3 with phosphoric acid 2: 1
Add % pTSA (to latex)

[0067]

[Table 13]

1: Adding 1% pTSA (to latex)

[0069]

[Table 14]

1: Addition of 1% pTSA (to latex) The main features and embodiments of the present invention are as follows. 1. Regarding the total weight of the composition, formula (a)

[0071]

[C4]

An alkylacrylamide glycolate of the formula wherein R1 is hydrogen or methyl, preferably hydrogen, and R2 and R3 are independently selected from C1-C6 alkyl and C5-C6 cycloalkyl.
0.1-25% by weight of alkyl ethers, (b) 50-95% by weight of vinyl acetate, (c) 0.1-25% by weight of monomers with one or more hydroxy functional groups.
, (d) a composition comprising an emulsion copolymer with 0 to 50% by weight of other vinyl monomers.

2. Component (a) is 0.5 to 10% by weight, component (b) is 80 to 90% by weight, and component (c) is 0.5 to 1% by weight.
0% by weight, and component (d) is 5 to 40% by weight.
Compositions as described in Section.

3. Component (a) is methylacrylamide
Glycolate methyl ether, component (c)
is selected from the group consisting of 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, polyvinyl alcohol, cellulose compounds and mixtures thereof, and component (d) is butyl acrylate, methyl methacrylate, dimethyl maleate, vinyl chloride, vinylidene chloride, A composition according to paragraph 1, selected from the group consisting of butadiene, ethylene, propylene, or mixtures thereof.

4. In the method of applying an adhesive composition between two layers to be bonded and pressing the layers coated with the adhesive composition to each other to bond them with an adhesive, the composition described in item 1 above is applied as an adhesive. Improved method.

5. A method for producing a polymer composition according to item 1 above, wherein component (a) is added to the polymerization medium by a power addition method to distribute the component uniformly over the backbone of the polymer.

6. Copolymer (a) 0.5 to 10% by weight
MAGME and (b) 50-95% by weight vinyl acetate.

Claims (3)

[Claims] 1. With respect to the total weight of the composition, (a) is a compound of the formula: wherein R1 is hydrogen or methyl, preferably hydrogen, and R2 and R3 are independently C1-C6 alkyl and C
(b) 50-95% by weight of vinyl acetate; (c) one or more hydroxy functional groups; 0.1 to 25% by weight of monomers with (d) 0 other vinyl monomers
A composition characterized in that it consists of ~50% by weight of emulsion polymerization. 2. Component (a) is 0.5 to 10% by weight, component (b) is 80 to 90% by weight, and component (c) is 0.5 to 1% by weight.
The composition according to claim 1, characterized in that the amount of component (d) is 5 to 40% by weight. 3. Component (a) is methylacrylamide glycolate methyl ether; component (c) is selected from the group consisting of 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, polyvinyl alcohol, cellulose compounds and mixtures thereof; Component (d)
Butyl acrylate, methyl methacrylate, dimethyl maleate, vinyl chloride, vinylidene chloride, butadiene,
The composition of claim 1, wherein the composition is selected from the group consisting of ethylene, propylene, or mixtures thereof.